Certain 2-(2-substituted benzoyl)-1,3,5-cyclohexanetriones

ABSTRACT

Compounds of the formula   &lt;IMAGE&gt;   wherein R60 is halogen, C1-C4 alkoxy, C1-C4 alkyl, C1-C4 haloalkyl, cyano, nitro, S(O)nR wherein R is C1-C4 alkyl and n is the integer 0, 1 or 2; and R61 through R66 are hydrogen or certain substituents, their salts, herbicidal compositions containing the compound or salts and the herbicidal use thereof.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part application of Ser. No. 110,988, filed Oct. 21, 1987, which is a divisional application of Ser. No. 880,370, filed June 30, 1986, which is a continuation-in-part application of Ser. No. 872,067, filed June 9, 1986 now abandoned.

Applicants specifically incorporate by reference the contents of the above listed U.S. patent applications.

BACKGROUND OF THE INVENTION

Compounds having the structural formula ##STR2## wherein X can be alkyl, n can be 0, 1, or 2, and R₁ can be phenyl or substituted phenyl are described in Japanese Patent Application No. 84632-1974 as being intermediates for the preparation of herbicidal compounds of the formula ##STR3## wherein R₁, X, and n are as defined above and R₂ is alkyl, alkenyl, or alkynyl. Specifically taught herbicidal compounds of this latter group are those where n is 2, X is 5,5-dimethyl, R₂ is allyl and R₁ is phenyl, 4-chlorophenyl or 4-methoxyphenyl.

The precursor intermediates for these three specifically taught compounds have no or almost no herbicidal activity.

DESCRIPTION OF THE INVENTION

Embodiment G of this invention relates to 2-benzoyl-1,3,5-cyclohexanetriones and their use as herbicides.

Embodiment G' of this invention is an herbicidal composition comprising an herbicidally active 2-benzoyl-substituted-1,3,5-cyclohexanetrione and an inert carrier therefor. The 4- and 6-positions of the 1,3,5-cyclohexanetrione moiety are preferably substituted with groups hereinafter defined, most preferably with all methyl groups. The benzoyl moiety can be substituted, preferably with the groups hereinafter recited.

The novel compounds of Embodiment G have the following structural formula ##STR4## wherein R⁶⁰ is hydrogen; halogen; C₁ -C₂ alkyl, preferably methyl; C₁ -C₂ alkoxy, preferably methoxy; nitro; cyano; C₁ -C₂ haloalkyl, preferably trifluoromethyl; R^(a) SO_(n) - wherein n is 0 or 2, preferably 2 and R^(a) is C₁ -C₂ alkyl, preferably methyl, trifluoromethyl or difluoromethyl; or trifluoromethoxy or difluoromethoxy. Preferably, R⁶⁰ is chlorine, bromine, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, trifluoromethyl, cyano, nitro, C₁ -C₂ alkylthio or C₁ -C₂ alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethyl or methylsulfonyl; and

R⁶¹ is hydrogen or C₁ -C₄ alkyl, preferably methyl;

R⁶² is hydrogen or C₁ -C₄ alkyl, preferably methyl; or

R⁶¹ and R⁶² together are C₂ -C₅ alkylene;

R⁶³ is C₁ -C₄ alkyl, preferably methyl;

R⁶⁴ is C₁ -C₄ alkyl, preferably methyl; or

R⁶³ and R⁶⁴ together are C₂ -C₅ alkylene;

R⁶⁵ and R⁶⁶ independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4) C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b) SO_(n) - wherein n is the integer 0, 1 or 2, preferably 2; and R^(b) is (a) C₁ -C₄ alkyl, preferably methyl; (b) C₁ -C₄ alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoromethyl or cyanomethyl; (c) phenyl; or (d) benzyl; (10) -NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; (12) -SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; or (13) -N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined.

Preferably R⁶⁵ is in the 3-position or 5-position. More preferably R⁶⁵ is hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C₁ -C₄ alkoxy, C₁ -C₄ alkyl or C₁ -C₄ thioalkyl. Preferably R⁶⁶ is in the 4-position. Most preferably R⁶⁶ is halogen, cyano, trifluoromethyl, or R^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl, preferably methyl or C₁ -C₄ haloalkyl, preferably chloromethyl, difluoromethyl or trifluoromethyl.

The term "C₁ -C₄ alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includes chlorine, bromine, iodine and fluorine. The terms "C₁ -C₄ alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term "C₁ -C₄ haloalkyl" includes the alkyl groups defined above under C₁ -C₄ alkyl in which one or more hydrogens is replaced by chlorine, bromine, iodine or fluorine.

Salts of the above-described compounds (as defined hereinafter) are included within the scope of the instant invention.

The compounds of this invention can have the following four structural formulae because of tautomerism: ##STR5## wherein R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵ and R⁶⁶ are as defined above.

The circled proton on each of the for tautomers is reasonably labile. These protons are acidic and can be removed by reaction with a base to form a salt having an anion of the following four resonance forms: ##STR6## wherein R⁶.spsp.0, R⁶.spsp.1, R⁶.spsp.2, R⁶.spsp.3, R⁶.spsp.4, R⁶.spsp.5 and R⁶.spsp.6 are as defined above.

Examples of cations of these bases are inorganic cations such as alkalimetals, e.g., lithium, sodium and potassium; the alkaline earth metals, e.g. calcium and magnesium or ammonium or organic cations such as substituted ammonium, sulfonium, sulfoxonium or phosphonium wherein the substituents and aliphatic or aromatic groups.

Those skilled in the art will recognize in considering the salts of this invention that varying degrees os association between the anion and cation will exist depending upon the nature of the cation. In some instances with a suitable cation, such as copper, the salt can exist in a chelated form.

The compounds of this invention and their salts are active herbicides of a general type. That is, they are herbicidally effective against a wide range of plant species. The method of controlling undesirable vegetation of the present invention comprises applying an herbicidally effective amount of the above-described compounds to the area where control is desired.

The compounds of Embodiment G and G' of the present invention can be prepared by the following two-stop general method.

The process proceeds via the production of an enol ester intermediate as shown in reaction (1). The final product is obtained by rearrangement of the enol ester as shown in reaction (2). The two reactions may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the enol ester, or in one step by inclusion of the cyanide source at the start of reaction (1). ##STR7## wherein R⁶⁰ through R⁶⁶ and moderate base are as defined and X is halogen, preferably chlorine, C₁ -C₄ alkyl-C(O)--O--, C₁ -C₄ alkoxy-C(O)--O-- or ##STR8## wherein R⁶⁰, R⁶⁵ and R⁶⁶ in this portion of the molecule are identical with those in the reactant shown above and the moderate base is as defined, preferably tri-C₁ -C₆ alkylamine, alkali metal carbonate or alkali metal phosphate.

Generally, in step (1) mole amounts of the trione and substituted benzoyl reactant are used, along with a mole amount or excess of the base. The two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide. The base or benzoyl reactant preferably is added to the reaction mixture with cooling. The mixture is stirred at 0° C.-50° C. until the reaction is substantially complete. ##STR9## wherein the moderate base and R⁶⁰ through R⁶⁶ are as defined above.

Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the moderate base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably about 0.1 mole of the cyanide source (e.g., potassium cyanide or acetone cyanohydrin). The mixture is stirred in a reaction pot until the rearrangement is substantially complete at a temperature below 50° C., preferably about 20° C. to about 40° C., and the desired product is recovered by conventional techniques.

The term "cyanide source" refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion.

The process is conducted in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.

Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C₂ -C₅ aliphatic aldehydes such as acetaldehyde, propionalidehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin.

The cyanide source is used in an amount up to about 50 mole percent base on the enol ester. It may be used in as little as about 1 mole percent to produce an acceptable rate of reaction at about 40° C. on a small scale. Larger scale reactions give more reproducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred.

The process is conducted with a molar excess, with respect to the enol ester, of a moderate base. By the term "moderate base" is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively). Moderate bases suitable for use in this embodiment include both organic bases, e.g., trialkylamines such as triethylamine and inorganic bases such as alkali metal carbonates and phosphates. Suitable inorganic bases include potassium carbonate and trisodium phosphate.

The base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.

When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the crown ethers.

A number of different solvents are useful in this process, depending on the nature of the acid halide or the acylated product. A preferred solvent for this reaction is 1,2-dichloroethane. Other solvents which may be employed, depending on the reactants or products include toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).

In general, depending on the nature of the reactants and the cyanide source, the rearrangement may be conducted at temperatures up to about 50° C.

The above described substituted benzoyl chlorides can be prepared from the corresponding substituted benzoic acids according to the teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp. 767-769 (1967). ##STR10## wherein R⁶⁰, R⁶⁵ and R⁶⁶ are as previously defined.

The substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).

The following are three representative examples of the methods described therein. ##STR11## wherein R⁶⁰, R⁶⁵ and R⁶⁶ are as previously defined.

In reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR12## wherein R⁶⁰, R⁶⁵ and R⁶⁶ are as previously defined.

In reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR13## wherein R⁶⁰, R⁶⁵ and R⁶⁶ are as previously defined.

In reaction (c) the substituted toluene is heated to reflux in an aqueous solution of potassium permanganate for several hours. The solution is then filtered and the reaction product is isolated by conventional techniques.

The following example teaches the synthesis of a representative compound of Embodiment G and G' of this invention.

EXAMPLE 1-G,G' 2-(2'-Nitro-4'-chlorobenzoyl)-4,4,6,6-tetramethyl-1,3,5-cyclohexanetrione ##STR14##

2-Nitro-4-chlorobenzoyl chloride (2.2 g, 10 mmol) and 4,4,6,6-tetramethyl-1,3,5-cyclohexanetrione (1.8 g, 10 mmol) were dissolved in methylene chloride. Triethylamine was added and the resulting solution stirred at room temperature for 30 minutes. The solution was washed with 1 normal hydrochloric acid (1N HCl), and saturated sodium chloride (brine), dried over anhydrous magnesium sulfate (MgSO₄) and concentrated under vacuum. The residue was dissolved in 20 ml acetonitrile. Triethylamine (5 ml, 3.5 equivalents) and acetone cyanohyrdin (0.5 g, 0.6 equivalent) were added and the mixture stirred at room temperature for 4 hours. After dilution with ether, the solution was washed with 1N HCl and extracted with 5% K₂ CO₃. The basic extract was acidified with HCl and extracted with ether. The ether extract was washed with brine, dried over MgSO₄ and concentrated under vacuum, yielding 2.2 g of crude product.

The following are tables of certain selected compounds of Embodiment G' that are preparable according to the procedures described herein. Compound numbers are assigned to each compound and are used throughout the remainder of the application.

                                      TABLE I-G                                    __________________________________________________________________________      ##STR15##                                                                     Comp. No.                                                                            R.sup.60                                                                            R.sup.61                                                                          R.sup.62                                                                          R.sup.63                                                                          R.sup.64                                                                          R.sup.65                                                                            R.sup.66                                                                               m.p. °C.                            __________________________________________________________________________      1G   NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    H       112-117                                     2G.sup.(a)                                                                          NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-Cl     76-82                                      3G   Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SO.sub.2 CH.sub.3                                                                    176-179°                             4G   CH.sub.3                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SO.sub.2 C.sub.2 H.sub.5                                                             gum                                         5G   CF.sub.3                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-CF.sub.3                                                                             viscous oil                                 6G   NO.sub.2                                                                            CH.sub. 3                                                                         CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SO.sub.2 CH.sub.2 Cl                                                                 oil                                         7G   Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-F     gum                                         8G   Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-OC.sub.2 H.sub.5                                                                  4-SO.sub.2 C.sub.2 H.sub.5                                                             gum                                         9G   NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SO.sub.2 CH.sub.3                                                                    gum                                        10G   Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SCH.sub.3                                                                            gum                                        11G   CH.sub.3                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-NO.sub.2                                                                          H       gum                                        12G   I    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    H       gum                                        13G   OCH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-Cl    gum                                        14G   Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-OCH.sub.3                                                                         4-Br    gum                                        15G   NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SO.sub.2 nC.sub.3 H.sub.7                                                            gum                                        16G   NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SO.sub.2 N(CH.sub.3).sub.2                                                           gum                                        17G   NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-CN    148-150°                            18G   SO.sub.2 CH.sub.3                                                                   CH.sub.3                                                                          CH.sub. 3                                                                         CH.sub.3                                                                          CH.sub.3                                                                          H    H       gum                                        19G   NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-CF.sub.3                                                                             gum                                        20G   H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-Cl    gum                                        21G   H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SCF.sub.3                                                                            gum                                        22G   H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-OCF.sub.3                                                                            gum                                        23G   Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-Cl 4-SO.sub.2 C.sub.2 H.sub.5                                                             gum                                        24G   H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-C(O)CH.sub.3                                                                         gum                                        25G   H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SO.sub.2CH.sub.3                                                                     129-131                                    26G   H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SCH.sub.3                                                                             89-92                                     27G   H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-CF.sub.3                                                                             115-125                                    28G   H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-CN     87-95                                     __________________________________________________________________________      .sup.(a) prepared in Example 1G,G'.                                      

                                      TABLE I                                      __________________________________________________________________________      ##STR16##                                                                     Comp. No.                                                                            R    R.sup.1                                                                           R.sup.2                                                                           R.sup.3                                                                           R.sup.4                                                                           R.sup.5   R.sup.6                                                                              m.p. °C.                         __________________________________________________________________________     29    NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-F   115-118                                 30    NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-SCH.sub.3                                                                          119-123                                 31    Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-SC.sub.2 H.sub.5                                                                   oil                                     32    Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-SC.sub.3 H.sub.7                                                                   oil                                     33    Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-N(C.sub.2 H.sub.5)COCH.sub.3                                                           4-NO.sub.2                                                                           oil                                     34    Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-SC.sub.2 H.sub.5                                                                       4-SO.sub.2 C.sub.2 H.sub.5                                                           oil                                     35    NO.sub.2                                                                            H  H  CH.sub.3                                                                          CH.sub.3                                                                          H         H     145-149                                 36    Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-Cl  gum                                     37    Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         H     glass                                   38    Br   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         H     glass                                   39    Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          4-Cl      5-Cl  glass                                   40    Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-Cl      5-Cl  glass                                   41    CH.sub.3                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-CH.sub.3                                                                            76-79                                  42    CH.sub.3                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         H      60-61                                  43    Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         5-Br  100-105                                 44    Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-NO.sub.2                                                                            72-75                                  45    Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         5-NO.sub.2                                                                           103-105                                 46    NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         5-CH.sub.3                                                                           136-139                                 47    Br   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-OC.sub.2 H.sub.5                                                                       4-SC.sub.3 H.sub.7                                                                   oil                                     48    SCH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                          CH.sub. 3                                                                         CH.sub.3                                                                          3-OC.sub.2 H.sub.5                                                                       4-SCH.sub.3                                                                          oil                                     49    Br   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-OC.sub.2 H.sub.4 OCH.sub.3                                                             4-Br  oil                                     50    Br   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-OC.sub.2 H.sub.5                                                                       4-SO.sub.2 C.sub.3 H.sub.7                                                           oil                                     51    SOCH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-OCH.sub.3                                                                              4-SOCH.sub.3                                                                         135-142                                 52    NO.sub.2                                                                            C.sub.2 H.sub.5                                                                   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         H     108-112                                 53    NO.sub.2                                                                            C.sub.2 H.sub.5                                                                   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-CF.sub.3                                                                           glass                                   54    Cl   C.sub.2 H.sub.5                                                                   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-SO.sub.2 CH.sub.3                                                                  glass                                   55    Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         5-Cl   96-98                                  56    NO.sub.2                                                                            C.sub.2 H.sub.5                                                                   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-Cl  glass                                   57    Cl   C.sub.2 H.sub.5                                                                   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-Cl  glass                                   58    Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-Cl      4-Cl  105-110                                 59    Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-Br  glass                                   60    NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         5-Cl  125-128                                 61    Br   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-OC.sub.3 H.sub.7                                                                       4-SC.sub.2 H.sub.5                                                                   oil                                     62.sup.(b)                                                                           NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         H      80-85                                  63.sup.(c)                                                                           NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         H     oil                                     64.sup.(d)                                                                           NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-F   oil                                     __________________________________________________________________________      .sup.(b) As the sodium salt.                                                   .sup.(c) As the triethylammonium salt.                                         .sup.(d) As the potassium salt.                                          

HERBICIDAL SCREENING TESTS

As previously mentioned, the herein described compounds produced in the above-described manner are phytotoxic compounds which are useful and valuable in controlling various plant species. Selected compounds of this invention were tested as herbicides in the following manner.

Pre-emergence herbicide test: On the day preceding treatment, seds of seven different weed species are planted in loamy sand soil in individual rows using one species per row across the width of a flat. The seeds used are green foxtail (FT) (Setaria viridis, watergrass (WG) (Echinochloa crusgalli), wild oat (WO) (Avena fatua), annula morningglory (AMG) (Ipomoea lacunosa), velvetleaf (VL) (Abutilon theophrasti), Indian mustard (MD) (Brassica juncea) and yellow nutsedge (YNG) (Cyperus esculentus). Ample seeds are planted to give about 20 to 40 seedlings per row, after emergence, depending upon the size of the plants.

Using an analytical balance, 600 milligrams (mg) of the compound to be tested are weighed out on a piece of glassine weighing paper. The paper and compound are placed in a 60 milliliter (ml) wide-mouth clear bottle and dissolved in 45 ml of acetone or substituted solvent. Eighteen ml of this solution are transferred to a 60 ml wide-mouth clear bottle and diluted with 22 ml of a water and acetone mixture (19:1) containing enough polyoxyethylene sorbitan monolaurate emulsifier to give a final solution of 0.5% (v/v). The solution is then sprayed on a seeded flat on a linear spray table calibrated to deliver 80 gallons per acre (748 L/ha). The application rate is 4 lb/acre (4.48 Kg/ha).

After treatment, the flats are placed in the greenhouse at a temperature of 70° to 80° F. and watered by sprinkling. Two weeks after treatment, the degree of injury or control is determined by comparison with untreated check plants of the same age. The injury rating from 0 to 100% is recorded for each species as percent control with 0% representing no injury and 100% representing complete control.

The results of the tests are shown in the following Tables

                  TABLE II-G                                                       ______________________________________                                         Pre-Emergence Herbicidal Activity                                              Application Rate - 4.48 kg/ha                                                  Cmpd.                                                                          No.    FT     WG      WO    AMG    VL   MD    YNS                              ______________________________________                                          1G    100    100     90    100    100  100   80                                2G    100    100     90    100    100  100   80                                3G    100    100     90    100    100  100   80                                4G    100    100     90    100    100  100   80                                5G    100    100     90    100    100  100   80                                6G*   100    100     100   100    100  --    20                                7G    100    100     80    100    100  100   80                                8G    85     100     80    100    100  100   80                                9G    100    100     80    100    100  100   80                               10G    100    100     80    100    100  100   80                               11G    100    100     80    100    100  100   80                               12G    100    100     80    90     100  100   0                                13G    100    100     70    100    100  100   0                                14G    100    100     75    100    100  100   90                               15G    100    100     80    100    100  100   90                               16G    100    100     90    100    100  100   80                               17G    100    100     80    100    100  100   80                               18G    100    100     90    85     100  100   80                               19G    100    100     100   100    100  100   80                               20G    70     95      10    100    100  100   0                                21G    100    100     100   100    100  100   80                               22G    100    100     90    100    100  100   80                               23G    100    100     100   100    100  100   80                               24G    0      80      0     25     80   70    0                                25G    100    100     80    100    100  100   80                               26G    100    100     100   80     100  100   80                               27G    100    100     100   100    100  100   80                               28G    100    100     90    100    100  100   80                               29     100    100     100   100    100  100   80                               30     100    100     100   100    100  100   100                              31     100    100     100   100    100  100   80                               32     100    100     100   100    100  100   80                               33     100    100     85    40     100  100   60                               34     100    100     100   95     100  100   80                               47     100    100     100   100    100  100   80                               48     100    100     100   100    100  100   80                               49     100    100     100   100    100  100   80                               50     100    100     100   100    100  100   80                               51     100    100     100   100    100  100   80                               52     100    100     100   100    100  100   80                               53     100    100     100   100    100  100   100                              58     100    100     100   100    100  100   80                               60     100    100     100   100    100  100   80                               62     100    100     100   100    100  100   80                               63     100    100     100   100    100  100   80                               64     100    100     100   100    100  100   80                               ______________________________________                                          A blank (--) indicates that the weed was not tested.                           *Tested at 0.56 kg/ha.                                                   

Post-Emergence Herbicide Test: This test is conducted in an identical manner to the testing procedure for the pre-emergence herbicide test, except the seeds of the seven different weed species are planted 10-12 days before treatment. Also, watering of the treated flats is confined to the soil surface and not to the foliage of the sprouted plants.

The results of the post-emergence herbicide test are reported in Table III.

                  TABLE III-G                                                      ______________________________________                                         Post-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                  Cmpd.                                                                          No.    FT     WG      WO   AMG    VL   MD    YNG                               ______________________________________                                          1G    100    95      90   90     100  100   80                                 2G    100    100     100  100    100  100   80                                 3G    100    100     95   100    100  100   90                                 4G    100    100     100  100    100  100   90                                 5G    100    100     100  100    100  100   100                                6G*   10     80      50   75     40   --    0                                  7G    70     75      70   90     90   80    80                                 8G    50     80      70   90     90   80    30                                 9G    70     80      70   90     90   80    30                                10G    75     80      70   80     60   50    70                                11G    70     80      70   80     80   80    80                                12G    100    75      90   75     80   80    80                                13G    60     70      70   100    100  100   80                                14G    20     70      40   60     80   80    70                                15G    90     70      70   75     80   90    70                                16G    50     70      80   60     80   90    70                                17G    90     60      70   65     80   80    80                                18G    30     50      80   95     95   80    70                                19G    100    100     95   90     100  100   80                                20G    10     40      5    70     80   90    70                                21G    95     90      95   95     100  100   70                                22G    80     90      90   80     100  100   70                                23G    90     80      80   80     90   80    30                                24G    0      30      0    40     80   20    0                                 25G    0      20      0    10     10   20    0                                 26G    80     70      70   80     80   80    70                                27G    90     90      90   80     80   90    60                                28G    70     65      50   80     80   80    70                                29     90     80      60   80     80   80    80                                30     90     80      80   80     80   80    80                                31     100    80      80   80     90   80    80                                32     90     80      80   80     80   80    30                                33     30     50      60   40     60   30    0                                 34     100    100     85   100    100  100   30                                47     100    100     100  100    100  100   60                                48     100    100     100  100    100  100   70                                49     100    100     100  100    100  100   60                                50     100    100     100  100    100  100   50                                51     100    100     100  100    100  100   30                                52     100    100     100  100    100  100   80                                53     100    100     100  100    100  100   80                                58     100    100     100  100    100  100   90                                60     100    90      90   90     100  100   80                                62     100    80      60   80     90   80    80                                63     90     80      60   80     90   80    80                                64     100    80      60   90     90   90    80                                ______________________________________                                          A blank (--) indicates the weed was not tested.                                *Tested at 0.56 kg/ha.                                                   

Pre-Emergence Multi-Weed Herbicide Test

Several compounds were evaluated at an application rate of 0.25 lb/acre (0.275 kg/ha) for pre-emergence activity against a larger number of weed species.

The process was generally similar to the pre-emergence herbicide test described above except that only 37.5 milligrams of test compound were weighed out and the application rate was 40 gallons per acre.

Indian mustard (MD) was eliminated in this test and the following weed species were added:

    ______________________________________                                         Grasses:                                                                              annual ryegrass                                                                               Lolium multiflorum                                                                           (ARG)                                             rox-orange sorghum                                                                            Sorghum bicolor                                                                              (SHC)                                             broadleaf signalgrass                                                                         Brachiaria platyphylla                                                                       (BSG)                                             hemp sesbania  Sesbania exaltata                                                                            (SESB)                                            nightshade     Solanum sp.   (SP)                                              cocklebur      Xattiium sp.  (CB)                                       ______________________________________                                    

The results of this 0.275 kg/ha test are shown in Table IV-G.

POST-EMERGENCE MULTI-WEED HERBICIDE TEST

Several compounds were evaluated at an application rate of 0.25 lb/acre (0.275 kg/ha) for post-emergence activity against the larger number of weed species that are used in the pre-emergent multi-herbicide test.

The process was generally similar to the post-emergence herbicide test described above except that only 37.5 milligrams of test compound were weighed out and the application rate was 40 gallons per acre.

The results of this 0.275 kg/ha test are shown in Table V-G.

                                      TABLE IV-G                                   __________________________________________________________________________     Pre-Emergence Multi-Weed Herbicidal Activity                                   Application Rate - 0.275 kg/ha                                                 Cmpd.                                                                          No. FT ARG WG SHC                                                                               WO BSG                                                                               AMG SESB                                                                               VL SP YNS                                                                               CB                                     __________________________________________________________________________     35  0  0   0  0  0  0  0   0   20 0  0  0                                      36  100                                                                               0   100                                                                               40 40 70 100 90  100                                                                               0  90 35                                     37  100                                                                               80  100                                                                               100                                                                               100                                                                               90 100 100 100                                                                               50 100                                                                               100                                    38  100                                                                               60  100                                                                               90 100                                                                               75 85  100 100                                                                               25 95 100                                    39  95 100 100                                                                               90 100                                                                               50 100 100 100                                                                               20 10 100                                    40  100                                                                               70  100                                                                               60 50 15 90  100 100                                                                               10 40 20                                     41  95 0   70 25 0  0  95  70  75 25 75 70                                     42  65 15  95 25 10 40 40  50  100                                                                               0  90 30                                     43  100                                                                               20  85 100                                                                               100                                                                               70 100 100 100                                                                               0  90 100                                    44  0  0   100                                                                               30 50 20 75  100 100                                                                               0  20 10                                     45  50 0   0  10 0  0  80  0   100                                                                               0  15 40                                     46  100                                                                               10  100                                                                               75 0  30 100 100 100                                                                               0  100                                                                               100                                    54  5  40  100                                                                               40 30 90 98  90  100                                                                               0  50 10                                     55  25 5   100                                                                               95 80 85 100 60  100                                                                               0  80 20                                     56  98 20  95 90 60 50 90  20  100                                                                               0  70 30                                     57  0  0   90 75 5  10 80  20  100                                                                               0  10 20                                     __________________________________________________________________________      (--) = Not Tested.                                                       

                                      TABLE VI-A                                   __________________________________________________________________________     Post-Emergence Multi-Weed Herbicidal Activity                                  Application Rate - 0.25 kg/ha                                                  Cmpd.                                                                          No. FT ARG WG SHC                                                                               WO BSG                                                                               AMG SESB                                                                               VL SP YNS                                                                               CB                                     __________________________________________________________________________     35  0  0   15 0  10 0  0   20  35 0  0  0                                      36  100                                                                               0   85 35 35 85 100 100 100                                                                               25 35 100                                    37  90 15  90 25 90 85 100 85  100                                                                               60 40 100                                    38  100                                                                               20  70 30 60 70 95  90  95 10 70 100                                    39  40 80  90 25 95 90 100 90  80 35 35 --                                     40  60 70  90 15 75 70 75  85  50 10 50 75                                     41  80 0   90 0  0  35 80  75  75 50 30 85                                     42  30 0   75 25 10 25 75  90  90 10 40 75                                     43  90 0   98 35 95 95 100 100 95 20 20 100                                    44  10 0   25 10 15 0  10  30  20 10 0  0                                      45  40 0   60 25 0  0  40  30  15 0  0  10                                     46  100                                                                               0   95 10 0  0  85  95  100                                                                               0  95 --                                     54  80 15  75 25 75 85 90  95  90 20 30 90                                     55  95 5   80 25 90 85 95  100 100                                                                               0  50 100                                    56  100                                                                               10  95 50 90 75 100 95  100                                                                               50 30 --                                     57  80 0   50 10 0  10 80  100 100                                                                               10 15 60                                     __________________________________________________________________________      (--) = Not Tested.                                                       

The compounds of the present invention and their salts are useful as herbicides and can be applied in a variety of ways at various concentrations. In practice, the compounds or salts are formulated into herbicidal compositions, by admixture, in herbicidally effective amounts, with the adjuvants and carriers normally employed for facilitating the dispersion of active ingredients for agricultural applications, recogizing the fact that the formulation and mode of application of a toxicant may affect the activity of the materials in a given application. Thus, these active herbicidal compounds or salts can be formulated as granules of relatively large particle size, as wettable powders, as emulsifiable concentrates, as powdery dusts, as flowables, as solutions or as any of several other known types of formulations, depending upon the desired mode of application. These formulations may contain as little as about 0.5% to as much as about 95% or more by weight active ingredient. A herbicidally effective amount depends upon the nature of the seeds or plants to be controlled and the rate of application varies from about 0.01 to approximately 10 pounds per acre, preferably from about 0.02 to about 4 pounds per acre.

Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersants. The wettable powder is ultimately applied to the soil either as a dry dust or as a dispersion in water or other liquid. Typical carriers for wettable powders include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic diluents. Wettable powders normally are prepared to contain about 5% to about 95% of the active ingredient and usually also contain a small amount of wetting, dispersing, or emulsifying agent to facilitate wetting and dispersion.

Emulsifiable concentrates are homogeneous liquid compositions which are dispersible in water or other dispersant, and may consist entirely of the active compound or salt with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthal, isophorone and other non-volatile organic solvents. For herbicidal application, these concentrates are dispersed in water or other liquid carrier and normally applied as a spray to the area to be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be appoied, but in general comprises about 0.5% to 95% of active ingredient by weight of the herbicidal composition.

Granular formulations wherein the toxicant is carried on relatively coarse particles, are usually applied witout dilution to the area in which suppression of vegetation is desired. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite and other organic or inorganic materials which absorb or which may be coated with the toxicant. Granular formulations normally are prepared to contain about 0.1% to about 25% of active ingredients which may include surface-active agents such heavy aromatic naphthas, kerosene or other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.

Typically wetting, dispersing or emulsifying agents and adjuvants used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their salts; polyhydric alcohols; polyethoxylated alcohols, esters and fatty amines; and other types of surface-active agents, many of which are available in commerce. The sufface-active agent, when used, normally comprises from 0.1% to 30% by weight of the herbicidal composition.

Dusts, which are free-flowing admixtures of the active ingredients with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers for the toxicant, are useful formulations for soil-incorporating application.

Pastes, which are homogeneous suspensions of a finely divided solid toxicant in a liquid carrier such as water or oil, are employed for specific purposes. These formulations normally contain about 5% to about 95% of active ingredient by weight, and may also contain small amounts of a wetting, dispersing or emulsifying agent to facilitate dispersion. For application, the pastes are normally diluted and applied as a spray to the are to be affected.

Other useful formulations for herbicidal applications include simple solutions of the active ingredient in a dispersant in which it is completely soluble at the desired concentration, such as water, acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized sprays, typically aerosols, wherein the active ingredient is dispersed in finely-divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freons, may also be used.

The phytotoxic compositions of this invention can be applied to the plants in the convenient manner. Thus, the dust and liquid compositions can be applied to the plant by the use of power-dusters, boom and hand sprayers and spray dusters. The compositions can also be applied from airplanes as a dust or a spray or by rope wick applications because they are effective in very low dosages. In order to modify or control growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions can be applied to the soil according to conventional methods and can be distributed in the soil to a depth of at lest 1/2 inch below the soil surface. It is not necessary that the phytotoxic composition be mechanically admixed with the soil particles since these compositions can also be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations. In the following examples the herbicidal compound can be substituted with the herbicidal salt of the compound.

    __________________________________________________________________________     General Formula with Ranges                                                                         Specific Formula                                          __________________________________________________________________________     EMULSIFIABLE CONCENTRATE FORMULATIONS                                          Herbicidal compound                                                                           5-55  herbicidal compound                                                                          24                                          surfactant(s)  5-25  proprietary blend of oil-                                                                    10                                          solvent(s)     20-90 soluble sulfonates and                                                   100%  polyoxyethylene ethers                                                         polar solvent 27                                                               petroleum hydrocarbon                                                                        39                                                                             100%                                        WETTABLE POWDER FORMULATIONS                                                   herbicidal compound                                                                           3-90  herbicidal compound                                                                          80                                          wetting agent  0.5-2 sodium dialkyl naphthalene                                                                   0.5                                         dispersing agent                                                                              1-8   sulfonate                                                 diluent(s)     8.5-87                                                                               sodium lignosulfonate                                                                        7                                                          100%  attapulgite clay                                                                             12.5                                                                           100%                                        EXTRUDED GRANULAR FORMULATIONS                                                 herbicidal compound                                                                           1-20  herbicidal compound                                                                          10                                          binding agent  0-10  lignin sulfonate                                                                             5                                           diluent(s)     70-99 calcium carbonate                                                                            85                                                         100%                100%                                        FLOWABLE FORMULATIONS                                                          herbicidal compound                                                                           20-70 herbicidal compound                                                                          45                                          surfactant(s)  1-10  polyoxyethylene ether                                                                        5                                           suspending agent(s)                                                                           0.05-1                                                                               attagel       0.05                                        antifreeze agent                                                                              1-10  propylene glycol                                                                             10                                          antimicrobial agent                                                                           1-10  1,2-benzisothiazoline-3-one                                                                  0.03                                        antifoam agent 0.1-1 silicone defoamer                                                                            0.02                                        solvent        7.95-77.85                                                                           water         39.9                                                       100%                100%                                        __________________________________________________________________________

When salts are used as the active ingredient in the herbicidal compositions of this invention it is recommended to use salts that are agriculturally acceptable.

The phytotoxic compositions of this invention can also contain other additives, for example, fertilizers, other herbicides and other pesticides, used as adjuvant or in combination with any of the above-described adjuvants. Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea and superphosphate. 

What is claimed is:
 1. Compounds of the formula ##STR17## wherein R⁶⁰ is hydrogen; halogen; C₁ -C₂ alkyl; C₁ -C₂ alkoxy; nitro; cyano; C₁ -C₂ haloalkyl; or R^(a) SO_(n) - wherein n is 0 to 2 and R^(a) is C₁ -C₂ alkyl, trifluoromethyl or difluoromethyl; or trifluoromethoxy or difluoromethoxy;R⁶¹ is hydrogen or C₁ -C₄ alkyl; R⁶² is hydrogen or C₁ -C₄ alkyl; or R⁶¹ and R⁶² together are R₂ -C₅ alkylene; R⁶³ is C₁ -C₄ alkyl; R⁶⁴ is C₁ -C₄ alkyl; or R⁶³ and R⁶⁴ together are C₂ -C₅ alkylene; R⁶⁵ and R⁶⁶ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) - wherein n is the integer 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) -NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; or (12) -SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; and (13) -N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined and their salts.
 2. The compounds of claim 1 wherein R⁶⁰ is chlorine, hydrogen, bromine, methyl, methoxy, nitro, trifluoromethyl or methylsulfonyl; R⁶¹, R⁶², R⁶³ and R⁶⁴ are methyl; R⁶⁵ and R⁶⁶ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) - wherein n is the integer 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; or (12) SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; or (13) -N-(R^(c))C(O)R^(d) are as defined.
 3. The compounds of claim 2 wherein R⁶⁵ and R⁶⁶ are independently are hydrogen; chlorine; fluorine; bromine; methyl; C₁ -C₄ alkoxy; trifluoromethoxy; cyano; nitro; trifluoromethyl; R^(b) SO_(n) - wherein n is the integer 0 or 2 and R^(b) is methyl, chloromethyl, trifluoromethyl; ethyl or n-propyl, R^(e) C(O)- where R^(e) is C₁ -C₄ alkyl; or SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined and R⁶⁵ is in the 3-position or 5-position and R⁶⁶ is in the 4-position.
 4. The compounds of claim 2 wherein R⁶⁵ is hydrogen and R⁶⁶ is hydrogen, chlorine, bromine, fluorine, cyano, trifluoromethyl or R^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl or C₁ -C₄ haloalkyl.
 5. The compound of claim 2 wherein R⁶⁰ is nitro, R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen; and R⁶⁶ is hydrogen.
 6. The compound of claim 2 wherein R⁶⁰ is nitro; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen; and R⁶⁶ is 4-chlorine.
 7. The compound of claim 2 wherein R⁶⁰ is chlorine; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen and R⁶⁶ is 4-SO₂ CH₃.
 8. The compound of claim 2 wherein R⁶⁰ is methyl; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen and R⁶⁶ is 4-SO₂ C₂ H₅.
 9. The compound of claim 2 wherein R⁶⁰ is trifluoromethyl; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen and R⁶⁶ is 4-trifluoromethyl.
 10. The compound of claim 2 wherein R⁶⁰ is nitro, R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen and R⁶⁶ is 4-SO₂ CH₃.
 11. The compound of claim 2 wherein R⁶⁰ is hydrogen; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen; and R⁶ is 4-trifluoromethylthio.
 12. The compound of claim 2 wherein R⁶⁰ is nitro; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen and R⁶⁶ is 4-cyano.
 13. The compound of claim 2 wherein R⁶⁰ is nitro; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen and R⁶⁶ is 4-SO₂ -n-C₃ H₇.
 14. The compound of claim 2 wherein R⁶⁰ is nitro; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen; and R⁶⁶ is 4-trifluoromethyl.
 15. The compound of claim 2 wherein R⁶⁰ is chlorine; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is 3-ethoxy; and R⁶⁶ is 4-SO₂ CH₂ CH₃.
 16. The compounds of claim 2 wherein R⁶⁵ is hydrogen.
 17. The compounds of claim 3 wherein R⁶⁵ is hydrogen.
 18. An herbicidal composition comprising an herbicidally active 2-benzoyl-substituted-1,3,5-cyclohexanetrione compound of the formula ##STR18## wherein R⁶⁰ is hydrogen; halogen; C₁ -C₂ alkyl; C₁ -C₂ alkoxy; cyano; C₁ -C₂ haloalkyl; or R^(a) SO_(n) - wherein n is 0 or 2 and R^(a) is nitro; alkyl, trifluoromethyl or difluoromethyl; or trifluoromethoxy or difluoro-C₁ -C₂ methoxy;R⁶¹ is hydrogen or C₁ -C₄ alkyl; R⁶² is hydrogen or C₁ -C₄ alkyl; or R⁶¹ and R⁶² together are C₂ -C₅ alkylene; R⁶³ is C₁ -C₄ alkyl; R⁶⁴ is C₁ -C₄ alkyl; or R⁶³ and R⁶⁴ together are C₂ -C₅ alkylene; R⁶⁵ and R⁶⁶ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) - wherein n is the integer 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) -NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; or (12) -SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; and (13) -N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined and their salts and an inert carrier therefor.
 19. The composition of claim 18 wherein R⁶⁰ is hydrogen, chlorine, bromine, methyl, methoxy, nitro, trifluoromethyl or methylsulfonyl; R⁶¹, R⁶², R⁶³ and R⁶⁴ are methyl; R⁶⁵ and R⁶⁶ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) - wherein m is the integer 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) -NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; or (12) SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; or (13) -N-(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined.
 20. The composition of claim 19 wherein R⁶⁵ and R⁶⁶ are independently are hydrogen; chlorine; fluorine; bromine; methyl; C₁ -C₄ alkoxy; trifluoromethoxy; cyano; nitro; trifluoromethyl; R^(b) SO_(n) - wherein n is the integer 0 or 2 and R^(b) is methyl, chloromethyl, trifluoromethyl, ethyl, or n-propyl; R^(e) C(O)- where R^(e) is C₁ -C₄ alkyl; or SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined and R⁶⁵ is in the 3-position or 5-position and R⁶⁶ is in the 4-position.
 21. The composition of claim 19 wherein R⁶⁵ is hydrogen and R⁶⁶ is hydrogen, chlorine, bromine, fluorine, cyano, trifluoromethyl or R^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl or C₁ -C₄ haloalkyl.
 22. The composition of claim 19 wherein R⁶⁰ is nitro, R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen; and R⁶⁶ is hydrogen.
 23. The composition of claim 19 wherein R⁶⁰ is nitro; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen; and R⁶⁶ is 4-chlorine.
 24. The composition of claim 19 wherein R⁶⁰ is chlorine; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen and R⁶⁶ is 4-SO₂ CH₃.
 25. The composition of claim 19 wherein R⁶⁰ is methyl; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen and R⁶⁶ is 4-SO₂ C₂ H₅.
 26. The composition of claim 19 wherein R⁶⁰ is trifluoromethyl; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen and R⁶⁶ is 4-trifluoromethyl.
 27. The composition of claim 19 wherein R⁶⁰ is nitro, R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen and R⁶⁶ is 4-SO₂ CH₃.
 28. The composition of claim 19 wherein R⁶⁰ is hydrogen; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen; and R⁶⁶ is 4-trifluoromethylthio.
 29. The composition of claim 19 wherein R⁶⁰ is nitro; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen and R⁶⁶ is 4-cyano.
 30. The composition of claim 19 wherein R⁶⁰ is nitro; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen and R⁶⁶ is 4-SO₂ -n-C₃ H₇.
 31. The composition of claim 19 wherein R⁶⁰ is nitro; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen; and R⁶⁶ is 4-trifluoromethyl.
 32. The composition of claim 19 wherein R⁶⁰ is chlorine; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is 3-ethoxy; and R⁶⁶ is 4-SO₂ CH₂ CH₃.
 33. The compositions of claim 19 wherein R⁶⁵ is hydrogen.
 34. The compositions of claim 20 wherein R⁶⁵ is hydrogen.
 35. Compounds of the formula ##STR19## wherein R⁶⁰ is hydrogen; halogen; C₁ -C₂ alkyl; C₁ -C₂ alkoxy; nitro; cyano; C₁ -C₂ haloalkyl; or R^(a) SO_(n) - wherein n is 0 or 2 and R^(a) is C₁ -C₂ alkyl, trifluoromethyl or difluoromethyl; or trifluoromethoxy or difluoromethoxy;R⁶¹ is hydrogen or C₁ -C₄ alkyl; R⁶² is hydrogen or C₁ -C₄ alkyl; or R⁶¹ and R⁶² together are C₂ -C₅ alkylene; R⁶³ is C₁ -C₄ alkyl; R⁶⁴ is C₁ -C₄ alkyl; or R⁶³ and R⁶⁴ together are C₂ -C₅ alkylene; R⁶⁵ and R⁶⁶ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) - wherein n is the integer 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) -NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; or (12) -SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; and (13) -N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined. 